CN110841645A - Synthesis method of hierarchical nanostructure iron-doped nickel oxide anode electrolysis water oxygen evolution catalyst - Google Patents
Synthesis method of hierarchical nanostructure iron-doped nickel oxide anode electrolysis water oxygen evolution catalyst Download PDFInfo
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 17
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
The invention provides a synthesis method of a hierarchical nanostructure iron-doped nickel oxide anode electrolysis water oxygen evolution catalyst. Under the condition that the molar ratio of the iron precursor to the nickel precursor is 1:1-2, the NiFe-I catalyst is obtained. Under the condition that the molar ratio of the iron precursor to the nickel precursor is 1:2-3, the NiFe-II catalyst is obtained. The NiFe-II catalyst is subjected to cyclic voltammetry treatment in an amino borane solution to obtain island-shaped iron-doped nickel oxide ultrathin nanosheets with hierarchical structures, and the ultrathin nanosheets are marked as NiFe-III catalysts. Three different types of iron-doped nickel oxide catalysts synthesized by regulating and controlling the morphology of the hierarchical structure can effectively meet the requirements on different oxygen evolution rates of electrolyzed water. Compared with the prior art, the method provided by the invention has the advantages that the electrochemical active surface area is increased, the catalyst consumption is saved, the highly porous structure is formed, the mass transfer of water molecules to the surface of the electrode is promoted, the catalyst activity is obviously improved, the overpotential of the oxygen evolution reaction is reduced, and the preparation process of the catalytic electrode is simplified.
Description
Technical Field
The invention relates to a preparation method of a nanostructured metal oxide catalyst for water electrolysis and oxygen evolution, in particular to a synthesis method of a nanostructured iron-doped nickel oxide anode catalyst for water electrolysis and oxygen evolution.
Background
With the decreasing of fossil fuel reserves and the deepening of sustainable development concepts, the hydrogen energy market will form a hydrogen supply pattern mainly based on renewable energy sources in the near future (about 2050), and the electrolysis of water to produce hydrogen gas according to the huge reserves of the earth seawater will become the most effective hydrogen supply, so that the hydrogen energy market will be paid much attention to in the production of hydrogen energy. The efficiency of hydrogen production by water electrolysis depends greatly on the activity of the catalyst at the cathode and anode, especially the activity of the anodic oxygen evolution half-reaction, the kinetics of which are slowly related to the transfer of four electrons. Therefore, the method for synthesizing the oxygen evolution catalyst with high activity, stable structure, simple synthesis process, low cost and large output is developed, so that the reduction of the overpotential of the oxygen evolution reaction has a decisive role in improving the hydrogen production efficiency of the electrolyzed water.
At present, although various experimental means are used for synthesizing the novel high-activity anode oxygen evolution catalyst, the synthesis method is complicated, the price of raw materials is high, the cost is high, and the prepared catalyst has poor structural stability and short service life and is not easy to be industrially manufactured on a large scale. The research distances are still quite different from the industrial oxygen evolution reaction catalyst which can really obtain the technical indexes and the industrial synthesis method, so that the nickel/stainless steel mesh oxygen evolution catalyst with lower activity which is widely used in the current industrial electrolytic bath cannot be replaced. Compared with the high-activity nano-structure 3d transition metal phosphide and selenide electrolyzed water oxygen evolution catalyst synthesized by the current experiment, the synthesis cost, the raw material price, the structural stability, the electrolyte corrosion resistance and the service life of the 3d transition metal oxide catalyst are doubtless, and the large-scale industrialization requirement can be met.
Therefore, an oxygen evolution catalyst with high activity, low price and long service life needs to be found, a reliable synthesis process route with low cost is established, so that the method is beneficial to batch production and ensures the stable product quality, and has important significance for promoting the development of hydrogen production by water electrolysis and market demand.
Disclosure of Invention
1. The technical problem to be solved is as follows:
the existing method for synthesizing the novel high-activity anode oxygen evolution catalyst is complex, the raw materials are expensive and have high cost, and the prepared catalyst has poor structural stability and short service life and is not easy to be industrially manufactured on a large scale
2. The technical scheme is as follows:
in order to solve the problems, the invention provides a synthesis method of a hierarchical nanostructure iron-doped nickel oxide anode electrolysis water oxygen evolution catalyst, which comprises the following steps: the method comprises the following steps: fully dissolving ferric nitrate, nickel nitrate and urea in water to obtain a solution, wherein the concentrations of the ferric nitrate and the nickel nitrate in the solution are 0.025-0.200 mol/L and 0.075-0.600 mol/L respectively, keeping the molar ratio of an iron-nickel precursor in the solution to be 1: 1-3, and then transferring the solution to a stainless steel autoclave reactor with a polytetrafluoroethylene lining, wherein the volume of the solution is 2.5-3.5 times that of the solution; step two: entering a third step if the molar ratio of the iron to the nickel precursor is 1:1-2, and entering a fourth step if the molar ratio of the iron to the nickel precursor is 1: 2-3; step three: adding diethylene glycol with the volume equal to that of the solution into the stainless steel autoclave reactor lined with polytetrafluoroethylene, and then entering the step five; step four, adding ethanol with the volume 2-2.5 times of that of the solution into the stainless steel high-pressure autoclave reactor with the polytetrafluoroethylene lining, and then entering step five; step five: immersing 4-6 carbon paper with surface hydroxylation, which is treated at 70-80 ℃ for 1.5-2.5 hours by concentrated nitric acid with the concentration of 68-70%, into a reactant solution of an autoclave reactor, sealing the reactor, heating to any temperature between 120 ℃ and 150 ℃ for reaction for 15-25 hours, and cooling the reactorAfter the pressure is released at room temperature, taking the carbon paper covered with the ferronickel basic carbonate precursor out of the high-pressure kettle, fully washing the carbon paper for 2 to 4 times by using warm water at the temperature of 40 to 45 ℃, and drying the carbon paper for later use; step six: then putting the carbon paper finally obtained in the step five into the air at the temperature of 4-6 ℃ for min−1Heating to 300-400 ℃ at the temperature rising speed, and continuously heating for 1.5-2.5 hours at the temperature to obtain the iron-doped nickel oxide electrode with the hierarchical nano structure.
The iron-doped nickel oxide electrode with the hierarchical nano structure prepared by the synthesis method in the second step is a structural spherical superfine nanowire cluster which is marked as a NiFe-I catalyst.
And D, taking the iron-doped nickel oxide electrode with the hierarchical nanostructure prepared by the synthesis method in the step three as a hierarchical structure flower-shaped nanosheet, and marking as a NiFe-II catalyst.
The size of a primary nanowire ball of the NiFe-I catalyst is 0.6-1.5 mu m, the diameter of a secondary nanowire is 3.5-7.5 nm, and the atomic ratio of iron to nickel is 1: 4 and 1: 8 respectively.
The size of the primary nanoflower of the NiFe-II catalyst is 0.6-1 mu m, the thickness of the secondary nanosheet is 5-15 nm, and the molar ratio of iron to nickel in the NiFe-II catalyst is 1: 11-11.5.
And (3) continuously scanning the NiFe-II catalyst in 0.1-1M potassium hydroxide aqueous solution containing 0.01-0.1M amino borane at the temperature of 20-28 ℃ for 10-50 times of cyclic volt-ampere (CV) to obtain the island iron-doped nickel oxide ultrathin nanosheet with the hierarchical structure, which is marked as the NiFe-III catalyst.
The sweep initiation-termination potential range is-0.2-0.6 VRHE, sweep rate: 2-20 mV s-1.
The NiFe-III catalyst has a primary nano island size of 0.1-0.5 mu m2, a secondary nano sheet thickness of 1-2.5 nm, and a molar ratio of iron to nickel in the NiFe-III catalyst of 1: 10.5-11.
3. Has the advantages that:
compared with the prior art, the electrolyzed water oxygen evolution catalyst and the synthesis method thereof provided by the invention have the following advantages: due to the formation of the unique hierarchical nano structure and the small-size secondary structure, the electrochemical active surface area (the number of active sites) is increased, and the amount of the catalyst is saved; the formation of a highly porous structure promotes mass transfer of water molecules to the surface of the electrode, and simultaneously iron is doped into nickel oxide crystal lattices to generate a synergistic electronic effect; the characteristics obviously improve the activity of the catalyst and reduce the overpotential of the oxygen evolution reaction. The addition of the high-conductivity carbon paper carrier electrode in the reaction process leads to the direct formation of an integrated catalytic electrode after the reaction is finished, thereby simplifying the preparation process of the catalytic electrode; the slight fluctuation of the concentration of reactants and the reaction temperature does not influence the hierarchical nano structure, thereby ensuring the reliability of the preparation method and the stability of the performance of the catalyst; the size distribution range of the secondary structure of the product is narrow, the shape of the hierarchical nano structure is regular, and the stability and repeatability of the catalytic performance are ensured; the inert carbon paper carrier electrode in the reaction route has large one-time input, the catalytic electrode product has large yield and stable quality, and the preparation method lays a foundation for the application of the preparation method in industrial production. Therefore, the preparation method of the iron-doped nickel oxide/carbon paper electrode is suitable for large-scale industrial production and has extremely wide market prospect.
Drawings
FIG. 1 is (A) a low magnification Scanning Electron Microscope (SEM), (B) a high magnification Scanning Electron Microscope (SEM), (C) a Transmission Electron Microscope (TEM), and (D) a High Resolution Transmission Electron Microscope (HRTEM) image of a NiFe-I catalyst prepared according to example 3 of the present invention (the plane spacing of 2.123 Ǻ in the image is attributed to the (200) lattice plane of cubic NiFe-I). (E) An energy dispersive X-ray energy spectrum (SEM-EDX) chart (inset: element content scale), (F) an SEM-EDX element distribution image, and (G) an X-ray diffraction (XRD) chart.
FIG. 2 is a plot of the sweep rate of 5 mV s for (A) in 1M KOH aqueous solution at 65 ℃ for a NiFe-I catalyst prepared in example 3 of the present invention−1Linear sweep voltammogram for catalytic water splitting oxygen analysis reaction, (B) at 200 mA cm−1(ii) a chronopotentiometric curve at constant current density, (C) electrochemical impedance spectroscopy, (D) CV curves at different sweep rates for estimating the electric double layer capacitance of the NiFe-I catalyst electrode: (C dl) (E) for determining electrochemical activityCapacitance current plotted against sweep rate.
FIG. 3 is (A) a low magnification Scanning Electron Microscope (SEM), (B) a high magnification Scanning Electron Microscope (SEM), (C) a Transmission Electron Microscope (TEM), and (D) a High Resolution Transmission Electron Microscope (HRTEM) image of a NiFe-I catalyst prepared according to example 4 of the present invention (the plane spacing of 2.105 Ǻ in the image is attributed to the (200) lattice plane of cubic NiFe-I). (E) Energy dispersive X-ray energy (TEM-EDX) pattern (inset: elemental content scale), (F) X-ray diffraction (XRD) pattern.
FIG. 4 is a plot of the sweep rate of 5 mV s for (A) in 1M KOH aqueous solution at 65 ℃ for a NiFe-I catalyst prepared in example 4 of the present invention−1Linear sweep voltammogram for catalytic water splitting oxygen analysis reaction, (B) at 200 mA cm−1(ii) a chronopotentiometric curve at constant current density, (C) electrochemical impedance spectroscopy, (D) CV curves at different sweep rates for estimating the electric double layer capacitance of the NiFe-I catalyst electrode: (C dl) And (E) a plot of capacitance current versus sweep rate plotted for the determination of electrochemically active surface area.
FIG. 5 is (A) a low magnification Scanning Electron Microscope (SEM), (B) a high magnification Scanning Electron Microscope (SEM), (C) a Transmission Electron Microscope (TEM), and (D) a High Resolution Transmission Electron Microscope (HRTEM) image of the NiFe-II catalyst prepared in example 5 of the present invention (the plane spacing of 2.457 Ǻ in the image is attributed to the (111) lattice plane of cubic NiFe-II). (E) An energy dispersive X-ray energy spectrum (SEM-EDX) chart (inset: element content scale), (F) an SEM-EDX element distribution image, and (G) an X-ray diffraction (XRD) chart.
FIG. 6 is a plot of the sweep rate of 5 mV s for (A) in 1M KOH aqueous solution at 65 ℃ for a NiFe-II catalyst prepared in example 5 of the present invention−1Linear sweep voltammogram for catalytic water splitting oxygen analysis reaction, (B) at 200 mA cm−1(II) a chronopotentiometric curve at a constant current density, (C) an electrochemical impedance spectrum, (D) CV curves at different sweep rates, for estimating the NiFe-II catalyst electrodeElectric double layer capacitor (C dl) And (E) a plot of capacitance current versus sweep rate plotted for the determination of electrochemically active surface area.
FIG. 7 is (A) a low magnification Scanning Electron Microscope (SEM), (B) a high magnification Scanning Electron Microscope (SEM), (C) a Transmission Electron Microscope (TEM), and (D) a High Resolution Transmission Electron Microscope (HRTEM) image of the NiFe-III catalyst prepared in example 6 of the present invention (the plane separation of 2.451 Ǻ in the image is attributed to the (111) lattice plane of cubic NiFe-III). (E) An energy dispersive X-ray energy spectrum (SEM-EDX) chart (inset: element content scale), (F) an SEM-EDX element distribution image, and (G) an X-ray diffraction (XRD) chart.
FIG. 8 is a plot of the sweep rate of 5 mV s for (A) in 1M KOH aqueous solution at 65 ℃ for a NiFe-III catalyst prepared in example 6 of the present invention−1Linear sweep voltammogram for catalytic water splitting oxygen analysis reaction, (B) at 200 mA cm−1(ii) a chronopotentiometric curve at constant current density, (C) electrochemical impedance spectroscopy, (D) CV curves at different sweep rates for estimating the electric double layer capacitance of the NiFe-III catalyst electrode: (C dl) And (E) a plot of capacitance current versus sweep rate plotted for the determination of electrochemically active surface area.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention provides a synthesis method of a hierarchical nanostructure iron-doped nickel oxide anode electrolysis water oxygen evolution catalyst, which comprises the following steps: the method comprises the following steps: mixing ferric nitrate (Fe)2(NO3)3∙9H2O), nickel nitrate (Ni (NO)3)2·6H2O) and urea (NH)2CONH2) Fully dissolved in water to obtain a solution, wherein the molar ratio of the iron-nickel precursor in the solution is 1: 1-3, and then the solution is transferred into a stainless steel autoclave reactor with a polytetrafluoroethylene lining, the volume of the solution is 2.5-3.5 times.
The iron-doped nickel oxide catalytic electrode with the hierarchical nanostructure comprises three types, namely a spherical superfine nanowire cluster with the hierarchical structure, a NiFe-I catalyst, a flower-shaped nanosheet with the hierarchical structure, a NiFe-II catalyst, an island-shaped ultrathin nanosheet cluster with the hierarchical structure and a NiFe-III catalyst.
Under the condition that the molar ratio of the iron precursor to the nickel precursor is 1:1-2, the NiFe-I catalyst is obtained.
Under the condition that the molar ratio of the iron precursor to the nickel precursor is 1:2-3, the NiFe-II catalyst is obtained.
The NiFe-II catalyst is subjected to cyclic voltammetry treatment in an amino borane solution to obtain island-shaped iron-doped nickel oxide ultrathin nanosheets with hierarchical structures, and the ultrathin nanosheets are marked as NiFe-III catalysts.
Three different types of iron-doped nickel oxide catalysts synthesized by regulating and controlling the morphology of the hierarchical structure can effectively meet the requirements on different oxygen evolution rates of electrolyzed water.
Example 1
A synthesis method of a hierarchical nanostructure iron-doped nickel oxide anode electrolysis water oxygen evolution catalyst comprises the following steps: mixing 0.152-1.212 g of ferric nitrate, 0.109-2.617 g of nickel nitrate and 0.40 g of urea (NH)2CONH2) Fully dissolved in 20 ml of water, concentration of ferric nitrate: 0.0187-0.150 mol/L, nickel nitrate concentration: 0.0187-0.300 mol/L, keeping the mol ratio of iron salt to nickel salt to be 1:1 or 1:2, then adding the mixture into a 50 ml stainless steel autoclave reactor lined with polytetrafluoroethylene, adding 20 ml diethylene glycol into the stainless steel autoclave reactor for full mixing, and then treating 4-6 carbon papers (1 multiplied by 2.5 cm) with concentrated nitric acid, wherein the concentration of the concentrated nitric acid is 68-70%, and treating the carbon papers for 2 hours at 75℃ (1 multiplied by 2.5 cm)2) Immersing the carbon paper into a reactant solution of an autoclave reactor, sealing and heating the reactant solution to any temperature between 120 and 150 ℃, reacting the reactant solution for 20 hours, cooling the reactant solution to room temperature, taking out the carbon paper covered with the ferronickel basic carbonate precursor, washing the carbon paper in warm water at 40 to 45 ℃ for 3 times, drying the carbon paper for later use, and then putting the carbon paper in air at 5 ℃ for min−1The temperature is increased to any temperature within the range of 300-400 ℃ and is continuously heated for 2 hours at the temperature, so that the iron-doped nickel oxide spherical superfine nanowire cluster with the hierarchical nano structure, namely the NiFe-I catalyst, is obtained, and the diethylene glycol can effectively control the divisionThe shape and size of the iron-doped nickel oxide with the nano-grade structure.
Example 2
The synthesis method of the hierarchical nanostructure iron-doped nickel oxide anode electrolysis water oxygen evolution catalyst comprises the following steps: dissolving 0.152-1.212 g of ferric nitrate, 0.3272-2.617 g of nickel nitrate and 0.600 g of urea in 15 ml of water, wherein the concentration of the ferric nitrate is as follows: 0.025-0.200 mol/liter, nickel nitrate concentration: 0.075-0.600 mol/L, keeping the mol ratio of iron salt to nickel salt at 1: 3, adding 35 ml of ethanol into a stainless steel autoclave reactor, fully mixing, carrying out treatment on 4-6 carbon paper (1 × 2.5 cm) treated at 75 ℃ for 2 hours by using concentrated nitric acid, wherein the concentration of the concentrated nitric acid is 68-70%2) And (2) immersing the carbon paper into a reactant solution of an autoclave reactor, sealing and heating the reactant solution to any temperature between 120 and 150 ℃, reacting the reactant solution for 20 hours, cooling the reactant solution to room temperature, taking out the carbon paper covered with the ferronickel basic carbonate precursor, washing the carbon paper in warm water at 40 to 45 ℃ for 3 times, and drying the carbon paper for later use. Then placing the carbon paper in the air at 5 ℃ for min−1The temperature is increased to any temperature within the range of 300-400 ℃, the temperature is continuously increased for 2 hours at the temperature, and then the temperature is naturally cooled to room temperature, so that the iron-doped nickel oxide flower-shaped nanosheet with the hierarchical nanostructure, namely the NiFe-II catalyst, is obtained, and the ethanol can effectively control the shape and size of the iron-doped nickel oxide with the hierarchical nanostructure.
Example 3
Fully dissolving 0.606 g of ferric nitrate, 0.436 g of nickel nitrate and 0.40 g of urea in 20 ml of water to prepare solutions of which the concentrations of the ferric nitrate and the nickel nitrate are both 0.075 mol/L, and then adding the solutions into a 50 ml of stainless steel reaction kettle lined with polytetrafluoroethylene; adding 20 ml of diethylene glycol into the reaction kettle, fully mixing, and treating 4-6 carbon papers (1 multiplied by 2.5 cm) with concentrated nitric acid with the concentration of 68-70% at 75 ℃ for 2 hours2) Soaking the carbon paper into a reactant solution of an autoclave reactor, sealing, reacting at a constant temperature of 120 ℃ for 20 hours, cooling to room temperature, taking out warm water (40-45 ℃) from the carbon paper covered with the ferronickel basic carbonate precursor, washing for 3 times, drying, and then placing the carbon paper in air at 5 ℃ for min−1Is heated to 400 ℃ and is kept at the temperatureAnd (3) continuously heating for 2 hours, and naturally cooling to room temperature to obtain the iron-doped nickel oxide spherical superfine nanowire cluster with the hierarchical nanostructure shown in figure 1, wherein the diameter of the primary nanowire ball is 0.6-1.5 mu m, and the diameter of the secondary nanowire is 3.5-7.5 nm.
As shown in FIG. 1, from SEM (FIGS. 1A and 1B) and TEM images (FIG. 1C) of the NiFe-I catalyst prepared in the above examples, it can be seen that NiFe-I has morphology of hierarchical spherical ultrafine nanowire clusters at a molar ratio of Fe to Ni salt precursor of 1:1, HRTEM image (FIG. 1D) and XRD pattern (FIG. 1G) confirm that NiFe-I has the same face-centered cubic structure as NiO, SEM-EDX pattern (FIG. 1E), quantitative analysis (table in FIG. 1E) and SEM-EDX element distribution pattern (FIG. 1F) show that NiFe-I is composed of Fe, Ni, and O elements, the atomic ratio of Fe/Ni/O is 1.0: 4.0: 5.2, and that three elements of Fe, Ni, and O are uniformly distributed in the NiFe-I catalyst.
As shown in FIG. 2, the linear sweep voltammogram of the oxygen evolution reaction of the NiFe-I catalyst prepared in the above example gave an output current of 200 mA cm−2The overpotential of (2) is 0.50V (FIG. 2A); at a constant current density of 200 mA cm−2When the catalyst is used, the fluctuation range of the potential within 350 hours does not exceed 5 percent, which shows that the catalyst has extremely high catalytic oxygen evolution reaction stability (figure 2B); extremely small series resistance (3.55. omega. cm)2) And a charge transfer resistance (2.17. omega. cm)2) Indicating that the catalytic electrode has excellent conductivity and catalytic activity (fig. 2C); the slope of the slope in FIG. 2E is divided by 2 to obtainC dlIs 10.91 mF cm−2(via FIGS. 2D and 2E), where ΔjThe value passes through the potential middle point of the CV curve in FIG. 2D (0.95V)RHE) The cathode current and the anode current are added and summed. According to specific capacitanceC s= 0.04 mF cm−4The surface area of the NiFe-I catalyst is 272.75 cm2。
Example 4:
0.606 g of ferric nitrate, 0.872 g of nickel nitrate and 0.40 g of urea were fully dissolved in 20 ml of water to prepare solutions of 0.075 and 0.150 mol/l of both ferric nitrate and nickel nitrate, which were then added to a 50 ml stainless steel autoclave lined with polytetrafluoroethylene(ii) a Adding 20 ml of diethylene glycol into the reaction kettle, fully mixing, and treating 4-6 carbon papers (1 multiplied by 2.5 cm) with concentrated nitric acid with the concentration of 68-70% at 75 ℃ for 2 hours2) Immersing the carbon paper into a reactant solution of an autoclave reactor, sealing, reacting at a constant temperature of 120 ℃ for 20 hours, cooling to room temperature, taking out the carbon paper covered with the ferronickel basic carbonate precursor, washing in warm water at 40-45 ℃ for 3 times, drying, and then placing the carbon paper in air at 5 ℃ for min−1The temperature is increased to 400 ℃ at the temperature raising speed, the temperature is continuously increased for 2 hours, and then the temperature is naturally cooled to room temperature, so that the iron-doped nickel oxide spherical superfine nanowire cluster with the hierarchical nano structure shown in figure 1 is obtained, wherein the diameter of a primary nanowire ball is 0.6-1.5 mu m, and the diameter of a secondary nanowire is 3.5-7.5 nm.
As shown in FIG. 3, from SEM (FIGS. 3A and 3B) and TEM images (FIG. 3C) of the NiFe-I catalyst prepared in the above example, it can be seen that NiFe-I has morphology of hierarchical spherical ultrafine nanowire clusters at a molar ratio of Fe to Ni salt precursor of 1:2, and HRTEM image (FIG. 3D) and XRD pattern (FIG. 3F) confirm that NiFe-I has the same face-centered cubic structure as NiO, and the change in plane-to-plane spacing results from the change in doped Fe content as compared to the sample in FIG. 1D. TEM-EDX mapping (FIG. 3E) and quantitative analysis (Table in FIG. 3E) showed that NiFe-I is composed of Fe, Ni, and O elements (note: the Cu signal in FIG. 3E is from the copper mesh used for TEM observation), and the ratio of Fe/Ni/O atoms is 1.0: 7.3: 8.4.
As shown in FIG. 4, the linear sweep voltammogram of the oxygen evolution reaction of the NiFe-I catalyst prepared in the above example gave an output current of 200 mA cm−2The overpotential of (2) is 0.44V (FIG. 4A); at a constant current density of 200 mA cm−2When the catalyst is used, the fluctuation range of the potential within 400 hours does not exceed 5 percent, which shows that the catalyst has extremely high catalytic oxygen evolution reaction stability (figure 4B); extremely small series resistance (2.78. omega. cm)2) And a charge transfer resistance (1.43. omega. cm)2) The catalytic electrode is shown to have more excellent conductivity and catalytic activity (fig. 4C); the slope of the slope line in FIG. 4E is divided by 2 to obtainC dlIs 10.95 mF cm−2(FIGS. 4D and 4E), where ΔjThe value passes through the potential midpoint of the CV curve in FIG. 4D (0.95V)RHE) The cathode current and the anode current are added and summed. According to specific capacitanceC s= 0.04 mF cm−4The surface area of the NiFe-I catalyst is 273.75 cm2。
Example 5:
fully dissolving 0.606 g of ferric nitrate, 1.309 g of nickel nitrate and 0.60 g of urea in 15 ml of water to prepare solutions of 0.100 mol/L and 0.300 mol/L of ferric nitrate and nickel nitrate, and then adding the solutions into a 50 ml of stainless steel reaction kettle lined with polytetrafluoroethylene; adding 15 ml of ethanol into the reaction kettle, fully mixing, and treating 4-6 carbon papers (1 multiplied by 2.5 cm) with concentrated nitric acid with the concentration of 68-70% at 75 ℃ for 2 hours2) Immersing the carbon paper into a reactant solution of an autoclave reactor, sealing, reacting at a constant temperature of 120 ℃ for 20 hours, cooling to room temperature, taking out the carbon paper covered with the ferronickel basic carbonate precursor, washing in warm water at 40-45 ℃ for 3 times, drying, and then placing the carbon paper in air at 5 ℃ for min−1Heating to 400 ℃ at the heating speed, continuously heating for 2 hours at the temperature, and naturally cooling to room temperature to obtain the iron-doped nickel oxide flower-shaped nanosheet electrode with the hierarchical nanostructure as shown in fig. 5.
As shown in FIG. 5, from SEM (FIGS. 5A and 5B) and TEM images (FIG. 5C) of the NiFe-II catalyst prepared in the above example, it can be seen that NiFe-II has hierarchical flower-like nanosheet morphology at a molar ratio of Fe to Ni salt precursor of 1: 3, and HRTEM image (FIG. 5D) and XRD pattern (FIG. 5G) confirm that NiFe-II has the same face-centered cubic structure as NiO, and the plane-to-plane spacing of 2.457 Ǻ in the figure is attributed to the (111) lattice plane of cubic NiFe-II. SEM-EDX map (FIG. 5E), quantitative analysis (Table in FIG. 5E), and SEM-EDX elemental map (FIG. 5F) show that NiFe-II is composed of Fe, Ni, and O elements, the Fe/Ni/O atomic ratio is 1.0: 11.3: 12.5, and demonstrate uniform distribution of the three elements Fe, Ni, and O in the NiFe-II catalyst.
As shown in FIG. 6, the linear sweep voltammogram of the oxygen evolution reaction of the NiFe-II catalyst prepared in the above example gave an output current of 200 mA cm−2Has a overpotential of0.45V (fig. 6A); at a constant current density of 200 mA cm−2When the reaction time is short, the fluctuation range of the potential within 400 hours does not exceed 5 percent, which shows that the catalyst has extremely high catalytic oxygen evolution reaction stability (figure 6B); extremely small series resistance (3.70. omega. cm)2) And a charge transfer resistance (1.82. omega. cm)2) The catalytic electrode is shown to have more excellent conductivity and catalytic activity (fig. 4C); the slope of the slope line in FIG. 6E is divided by 2 to obtainC dlIs 11.06 mF cm−2(FIGS. 6D and 6E), where ΔjThe value passes through the potential midpoint of the CV curve in FIG. 6D (0.95V)RHE) The cathode current and the anode current are added and summed. According to specific capacitanceC s= 0.04 mF cm−4The surface area of the NiFe-I catalyst is 276.50 cm2。
Example 6:
the NiFe-II electrode prepared in the third example was subjected to continuous 25 Cyclic Voltammetry (CV) scans at room temperature (25 ℃) in 40 ml of 0.1M aqueous potassium hydroxide solution containing 0.05M aminoborane, with the start-stop potential range of-0.2-0.6VRHESweeping speed: 10 mV s−1And continuously washing the electrode with warm water at the temperature of 40-45 ℃ for 3 times, and drying to obtain the hierarchical iron-doped nickel oxide island-shaped ultrathin nanosheet cluster electrode shown in FIG. 7.
As shown in fig. 7, from SEM (fig. 7A and 7B) and TEM images (fig. 7C) of the NiFe-III catalyst prepared in the above example, it can be seen that the CV scanning electrochemical synthesis step, NiFe-III has a hierarchical structure island-shaped ultrathin nanosheet cluster morphology and a porous structure, HRTEM images (fig. 7D) and XRD patterns (fig. 7G) confirm that NiFe-III has the same face-centered cubic structure as NiO, and the plane-to-plane spacing of 2.451 Ǻ in the figure is attributed to the (111) lattice plane of cubic NiFe-III. SEM-EDX map (FIG. 7E), quantitative analysis (Table in FIG. 7E), and SEM-EDX elemental map (FIG. 7F) show that NiFe-III is composed of Fe, Ni, and O elements with an atomic ratio of Fe/Ni/O of 1.0: 10.8: 12.2, and demonstrate uniform distribution of the three elements Fe, Ni, O in the NiFe-III catalyst. The Fe/Ni/O atomic ratio remains substantially unchanged compared to the NiFe-II catalyst. The atomic force microscope image revealed that the thickness of the ultrathin nanosheets was 1-2.5 nm (FIG. 7H).
Referring to FIG. 8, the linear sweep voltammogram of the oxygen evolution reaction of the NiFe-III catalyst prepared in the above example gave an output current of 200 mA cm−2The overpotential of (2) is 0.42V (FIG. 8A); at a constant current density of 200 mA cm−2When the reaction time is short, the fluctuation range of the potential within 400 hours does not exceed 5 percent, which shows that the catalyst has extremely high catalytic oxygen evolution reaction stability (figure 8B); extremely small series resistance (2.41. omega. cm)2) And a charge transfer resistance (1.24. omega. cm)2) The catalytic electrode is shown to have more excellent conductivity and catalytic activity (fig. 8C); the slope of the slope line in FIG. 8E is divided by 2 to obtainC dlIs 20.84 mF cm−2(FIGS. 8D and 8E), where ΔjThe value passes through the potential middle point of the CV curve in FIG. 8D (0.95V)RHE) The cathode current and the anode current are added and summed. According to specific capacitanceC s= 0.04 mF cm−4The surface area of the NiFe-I catalyst is 521.00 cm2. Compared with NiFe-II and NiFe-II catalysts, the specific surface area of the NiFe-III catalyst is increased by 2 times due to the ultrathin film structure and the porous property of the NiFe-III catalyst, and the catalyst is a main factor for enhancing the catalytic activity of the oxygen evolution reaction.
In the above examples, the ferric nitrate used was nonahydrate and ferric nitrate, and the molecular formula was Fe2(NO3)3∙9H2O and nickel nitrate adopt hexahydrate and nickel nitrate, and the molecular formula is Ni (NO)3)2·6H2O。
The method can also be used for preparing NiO hierarchical nano-structure electrodes doped with other transition metal ions (such as Mn, Co and Cu).
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A process for synthesizing the hierarchical nano-class Fe-doped nickel oxide catalyst used for electrolyzing water to generate oxygenThe method comprises the following steps: the method comprises the following steps: fully dissolving ferric nitrate, nickel nitrate and urea in water to obtain a solution, wherein the concentrations of the ferric nitrate and the nickel nitrate in the solution are 0.025-0.200 mol/L and 0.075-0.600 mol/L respectively, keeping the molar ratio of an iron-nickel precursor in the solution to be 1: 1-3, and then transferring the solution to a stainless steel autoclave reactor with a polytetrafluoroethylene lining, wherein the volume of the solution is 2.5-3.5 times that of the solution; step two: entering a third step if the molar ratio of the iron to the nickel precursor is 1:1-2, and entering a fourth step if the molar ratio of the iron to the nickel precursor is 1: 2-3; step three: adding diethylene glycol with the volume equal to that of the solution into the stainless steel autoclave reactor lined with polytetrafluoroethylene, and then entering the step five; step four, adding ethanol with the volume 2-2.5 times of that of the solution into the stainless steel high-pressure autoclave reactor with the polytetrafluoroethylene lining, and then entering step five; step five: soaking 4-6 carbon papers with surface hydroxylation, which are treated for 1.5-2.5 hours at 70-80 ℃ by concentrated nitric acid with the concentration of 68-70%, into a reactant solution of an autoclave reactor, sealing the reactor, heating to any temperature in the range of 120-150 ℃ for reaction for 15-25 hours, cooling the reactor to room temperature for pressure relief, taking out the carbon paper covered with a ferronickel basic carbonate precursor from the autoclave, fully washing for 2-4 times by warm water with the temperature of 40-45 ℃, and drying for later use; step six: then putting the carbon paper finally obtained in the step five into the air at the temperature of 4-6 ℃ for min−1Heating to 300-400 ℃ at the temperature rising speed, and continuously heating for 1.5-2.5 hours at the temperature to obtain the iron-doped nickel oxide electrode with the hierarchical nano structure.
2. The method of claim 1, wherein: the iron-doped nickel oxide electrode with the hierarchical nano structure prepared by the synthesis method in the second step is a spherical superfine nanowire cluster with the hierarchical structure, and is marked as a NiFe-I catalyst.
3. The method of claim 1, wherein: and D, taking the iron-doped nickel oxide electrode with the hierarchical nanostructure prepared by the synthesis method in the step three as a hierarchical structure flower-shaped nanosheet, and marking as a NiFe-II catalyst.
4. The method of claim 2, wherein: the size of a primary nanowire ball of the NiFe-I is 0.6-1.5 mu m, the diameter of a secondary nanowire is 3.5-7.5 nm, and the atomic ratio of iron to nickel is 1: 4 and 1: 8 respectively.
5. The method of claim 3, wherein: the size of the primary nanoflower of the NiFe-II catalyst is 0.6-1 mu m, the thickness of the secondary nanosheet is 5-15 nm, and the molar ratio of iron to nickel in the NiFe-II catalyst is 1: 11-11.5.
6. The method of claim 1, 3 or 5, wherein: and (3) continuously scanning the NiFe-II catalyst in 0.1-1M potassium hydroxide aqueous solution containing 0.01-0.1M amino borane at the temperature of 20-28 ℃ for 10-50 times of cyclic volt-ampere (CV) to obtain the island iron-doped nickel oxide ultrathin nanosheet with the hierarchical structure, which is marked as the NiFe-III catalyst.
7. The method of claim 6, wherein: the sweep initiation-termination potential range is-0.2-0.6 VRHE, sweep rate: 2-20 mV s-1.
8. The method of claim 7, wherein: the primary nano island size of the NiFe-III catalyst is 0.1-0.5 mu m2The thickness of the second-level nanosheet is 1 nm-2.5 nm, and the molar ratio of iron to nickel in the NiFe-III is 1: 10.5-11.
9. The method of claim 6, wherein: the primary nano island size of the NiFe-III catalyst is 0.1-0.5 mu m2The thickness of the second-level nanosheet is 1 nm-2.5 nm, and the molar ratio of iron to nickel in the NiFe-III catalyst is 1: 10.5-11.
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